Monoacid salts of aralkyl polyamines and metallized monoazo dyestuffs



MONUACIHD SALTS OF ARALKYL PGLYAMINES AND METALLIZED MONOAZO DYESTUFFS No Drawing. Application October 2, 1953 Serial No. 383,926

6 Claims. (Cl. 260-147) This invention relates to monoacid salts of aralkyl polyamines and monoazo dyestuffs which are metallized with chromium or cobalt in such manner that the dye metal complex contains 2 molecules of dye for each atom of chromium or cobalt.

It is known that organic dyestuffs, containing as a water soluble substituent, either a sulfonic acid or a carboxylic acid group, or both, can be rendered soluble in organic solvents such as, alcohol, acetone, etc. by converting the water soluble group into a salt with an organic amine. While such dyes are soluble in organic solvents, they are not, however, completely insoluble in water. Most of them are partially or sparingly soluble in water. This solubility is highly undesirable because it leads to water-bleeding. The latter phenomenon is readily observed when such solvent solubilized dyestuffs are incorporated into nitrocellulose or vinyl lacquers, and the lacquer films exposed to wet treatment, such as Water or rain. After such treatment the dyestuff or color bleeds from the lacquer film. Such lacquer coatings cannot be applied to tin foil used on for example, milk bottle caps, Where the foil might come in contact with the milk.

We have found that when monoacid salts of N,N'-dibenzyl-N,N-dialkyl alkylenediamines or N,N"-dibenzyl- N,N,N"-trialkyldialkylene triamines and metallized monoazo dyestuffs devoid of sulfonic acid or carboxylic acid groups, which are metallized with chromium or cobalt in such manner that the dye-metal complex contains 2 molecules of dye for each atom of chromium or cobalt, are incorporated into lacquers, and the films of such lacquers exposed to or brought in contact with water, no water-bleeding occurs. The water insoluble monoacid dibenzyl polyamine salts of the metallized monoazo dyes are very soluble in alcohol, acetone, i. e. the usual lacquer solvents including various prepared lacquers. Because of their great solubility in lacquer solvents, the resulting lacquers from the monoacid amine salts possess greater tinctorial strength than the sodium salts of such metal-dye complexes.

While the formation of the metal complex increases the alcohol or acetone solubility of the dye, the polyamine monoacid salt formation further increases the solubility of the dye in lacquer solvents, the compounds of the present invention are outstanding in the great depths of shade which can be obtained in the lacquers.

We have also found that the monoacid polyamine salts of the metal complexes have greater alcohol and ketone solubility than the monoacid monoamine or polyamine salts of sulfonated (unmetallized) dyes.

The foregoing dyes are prepared by boiling 1 mole of the sodium salt of the metal lake of an o,o -dihydroxymonoazo dye in a large volume of water with 1 mole of N,N-dibenzyl-N,N-dialkyl ethylenediamine or 1 mole of N,N"-dibenZyl-N,N',N"-trialkyl-dialkylene triamine to which acetic acid has been added. The amine salt of the dye precipitates shortly after adding the acetic acid solution of the diamine or triamine and is filtered and dried.

As an alternative method, the free acid form of such Tnited States Patent "ice a metallized monoazo dye is dissolved in acetone. To the acetone solution the theoretical quantity of the diamine or triamine is added and then the acetone evaporated. The monoacid amine salt of the metallized monoazo dyestuif is obtained upon evaporation to dryness.

Detailed methods of preparing and applying these new coloring materials for nitrocellulose and vinyl lacquers will appear hereinafter.

Another method of application of these compounds is to prepare the monoacid amine salt of the dyestuff in the lacquer itself by adding the diamine or triamine to the lacquer in solution in alcohol or acetone, and then adding to the lacquer solution the acid form of the metallized monoazo dye. In such an application an excess of the diamine or triamine in the lacquer solution would have no deleterious effect.

The monoazo dyestuffs employed in the preparation of monoacid amine salts are characterized by the following general formula:

wherein Y represents a radical selected from the class consisting of hydrogen, lower alkyl, e. g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, etc., cyano and nitro radicals, and Z and Z represent coupling components, free of carboxylic or sulfonic acid groups, consisting of phenols, naphthols, or enolizable keto compounds which contain an OH group in ortho or alpha position to the azo bridge after coupling and before forming the metaldye complex. While Z and Z are usually the same, they may be different.

As illustrative examples of the phenols, :naphthols and enolizable keto compounds, the following may be mentioned:

Phenols:

p-Tertiarybutylphenol p-Cresol Resorcinol m-Diethylaminophenol 3acetylamino4-methylphenol 3acetylamino4-tertiarybutylphenol 3,4-dimethylphenol 2-tetralol Naphthols:

2-naphthol 3-sulfamyl-l-naphthol 6-sulfamyl-2-naphthol 2,8-dihydroxy-6-sulfamy1-naphthalene 4-methyl-1-naphthol 4-methoxy-l-naphthol Enolizable keto compounds:

Acetoacetanilide 2,4-dihydroxy-quinoline N-methyl-2,4-dihydroxy-quinoline Z-chloro-acetoacetanilide lphenyl-3-methyl-5-pyrazolone l- 3'-sulfamylphenyl) 3-methyl-5-pyrazolone l-(3-methylsulfonylphenyl)3-methyl-5-pyrazolone There is a large class of free acids and sodium salts of such dye-metal complexes and no difiiculty will be encountered by those skilled in the art in making the proper selection from the foregoing description.

The following is merely illustrative of such dye complexes which may be employed in accordance with the present invention:

. u I. Chrome complex of '4-(4'-nitro2'-hydroxyphenylazo)-3-methyl-l-phenyl-S-pyrazolone (chrome complex of the azo dye resulting from the diazotization of S-nitroinvention are enumerated in columns 3 and 4 of U. S. P. 2-aminopheno1 and coupled to 1-phenyl-3-methyl-5-py- 2,539,212. The N,N"-dibenzyl-N,N',N"-trialkyl-dialkylrazolone). 5 ene triamines including the various species thereof are II. Chrome complex of 4-(2'-carboxyphenylazo)-3- disclosed in U. S. P. 2,619,502. methyl-l-phenyl-S-pyrazolone (chrome complex of the azo By reference to the foregoing patents, one skilled in dye resulting from the diazotization of anthranilic acid this art will have no difliculty in selecting the proper and coupled to 1-phenyl-3-methyl-5-pyrazolone). polyamines, all of which may be successfully utilized in III. Cobalt complex of 2-[4'-nitro-2'-hydroxyphenyll preparing the final dyes. azol-2-acetoacetanilide (cobalt complex of the azo dye In the monoacid salts of aralkyl polyamines and monoresulting from the diazotization of S-nitro-Z-aminophenol azo dyestufiis prepared in accordance with the present inand coupled to acetoacetanil-ide). vention the salt linkage occurs between the metal com- IV. Cobalt complex of l-[4'-nitro-2'-hydroxyphenylplex and the amine. Our monoacid aralkyla'ted polyamine azo]-2-hydroxy-naphthalene (cobalt complex of the azo la salts, Which involve only one amino group of the polydye resulting from the diazotization of 5-nitro-2-aminoamine, are preferable to salts of metals, such as sodium phenol and coupled to ,B-naphthol). and potassium or to salts of monoamines, such as for V. Chrome complex of 1-[4'-nitro-2'-hydroxyphenylexample, dicyclohexylamine, diamylamine and the like, azoJ-Z-hydroxy-naphthalene (chrome complex of the azo because of the greater solubility of the aralkylated polydye resulting from the diazotizati-on of 5-nitro-2-aminoamine salts in various types of solvents employed in the phenol and coupled to fi-naphthol). preparation of lacquers over the monoarnine salts. In VI. Chrome complex of 1-[3'-5'-dinitro-2-hydroxyaddition, our salts exhibit an unusually high degree of phenylazoJ-Z-hydroxy tetralin (chrome complex of the alcohol and ketone solubility. This high solubility is a azo dye resulting from the diazotization of picramic acid prerequisite for obtaining heavy shades in nitrocellulose and coupled to fi-tetralol). and vnyl lacquer coatings. Thus, by preparing the mono- The N,N'-dibenzyl-N,N-dialkyl ethylenediamines (1) acid amine salts of these metal lacquers, both desirable and N,N"-dibenzyl-N,N',N"-trialkyl-diethylene triamines features of coloring matters for nitrocellulose and vinyl (2) which are utilized for the salt formation are characla quer are obtained together with complete insolubility terized by the following general formula: in water.

4 The N,N'-dibenzyl-N,N'-dialiphatic ethylene diamines, which may be employed in accordance with the present 1) The following examples which are merely illustrative will show how the present invention may be practiced. Example 1 (2) R R B The dye consists of the monoacid amine salt of N,N- dibenzyl-N,N'-dimethyl ethylenediamine with the free acid form of the dye Azosol Fast Red BE.

, CIlHI (I3 If-CHr-OHr-IIIH radical, i. e., phenyl, alkylphenyl, e. g., tolyl, ethylphenyl, 22.40 grams of the free acid form of the chrome combutylphenyl and the like, halogenophenyl, e. g. chloroplex of 5-nitro-2-aminophenol-3-methyl-5-pyrazolone were phenyl bromophenyl, dichlorophenyl, dibromophenyl, dissolved in 100 ml. of acetone. Then there were added etc., alkoxyphenyl, e. g., anisyl, ethoxyphenyl, propoxy- 75 ml. of 0.5 N sulfuric acid. To this mixture 200 ml. phenyl, etc., carbalkoxyphenyl, e. g., carbomethoxyof water were added, and the mixture heated until the phenyl carbethoxyphenyl, carbopropoxyphenyl, etc., arylacetone was evaporated. The material was filtered and oxyphenyl, e. g., phenoxyphenyl, methlyphenoxyphenyl washed with water. The presscake was added to a mixetc., cyanophenyl, etc.; R is an aliphatic radical, i. eture of 10.4 grams of N,N'-dibenzyl-N,N'-dimethyl ethylalkyl such as methyl, ethyl, propyl, butyl, amyl, hexyl, enediamine in 100 ml. of acetone. The material was heptyl and the like; alkellyl, Such as ly y l-mefllyl' stirred over a steam bath and allowed to evaporate. After B-butenyl, hexenyl and the like; alk-oxyalkyl, i. e. etho Y' all the acetone had evaporated, a small amount of moismethyl, methoxyethyl, rnethoxypropyl, ethoxyethyl and ture remained. The product was filtered and dried in a the like; hydroxyalkyl, 1. e., hydroxymethyl, hydroxyvacuum Oven at 5 ethyl hydroxypropyl hydroxybutyl, em; cyanoanfyl It is to be noted that the depth of shade will vary with g i gf ig i cyanoethylbcyangfropyl 3;? the i g the amount of dye pigment used. This amount may ya y 1. e., car ome oxyme y Car 6 xyrange from 100-400 mg. in the following compositions: methyl, carbopropoxymethyl, carbethoxyethyl and the 100 a f h h f like; and R represents an alkylene group, i. e., any ali- O t e dye M t e oregomg emfnple was healed phatic open chain linking component, Such as methylene, with 10 of methanol and 15 cc. of nitrocellulose thinethylene trimethylene, propylene and the like It is to nor consisting of 30 parts of toluene, 4? parts of ethanol, be noted, however, that the aliphatic radical represented and Parts of ethyl acetatemlxtllle Was Shaken by R should be free from halogen and solubilizing groups, r 10 minutes 011 a Shaking machine and 40 grams of e. g. carboxyl, sulfo, and the lik nitrocellulose lacquer consisting of 67% parts of nitro- .AI'CH2-I I-R1I TR|-&-CHr-AI wherein Ar is a substituted or unsubstituted phenyl type cellulose solution prepared as will be hereinafter de-" acetone was completely evaporated, whereupon the described. 19 parts of glyptal solution in 7.7 parts of disired dye was obtained in the form of a hard, dry mass. butyl phthalate, and 5.8 parts of n-butanol were added, The material was ground and thoroughly dried in an airand shaking continued for minutes. The resultant oven at 90 C. to give 32.0 grams of dry dye.

solution was coated on aluminum foil and also on white Application of the dye ofExample 2 and of all succeedclay coated paper bearing the name Krorne Kote, using ing examples was carried out in the same manner as that a Bird Film Applicator so adjusted as to form a film of of the dye of Example 1. The monoacid N,N',N"-triwet lacquer 0.003 inch thick. The drawdowns were almethyl-N,N"-dibenzyl diethylenetriamine salt of the lowed to dry in air, after which they were tested for rnetallized dye showed essentially no water-bleeding while strength, shade, light fastness, water-bleeding fastness, 10 the Sod m Salt of the same dye showed considerable The nitrocellulose solution utilized above, consisted of the following ingredients: Example 1 was repeated with the exception that 10.4 Y grams of N,N-dibenzyl-N,N'-dimethylethylenediamine gg ggfg 1/2 sec 2 were replaced by 11.04 grams of N,N-dibenzyl-(N-hy- Ethyle g gg 23 3o y y )e y i un I m acetate 9.6 The apphcation or this dye was carried out as m Ex- Butyl alcohol 5.8 ample 1 with the same results.

Example 4 I 2 H l C r- I C H:)1N-( C H2):-N-C Hr- C-N CH: (3H1 H: N==Nc o 0 \CH:

The monoacid N,N-dibenzyl-N,N'-dimethyl ethylene- I diamine salt of the free acid form of the metallized dye 28.3 grams of tie sodium salt of the chrome complex of COIIIPIEX of the azo dye resulting from diazotiza' the dye: 4-nitro-2-aminophenol-e acetoacetanilide were tion of S'mtmZ'ammOPheHOI and coupling to l'phenyl' dissolved in 100 ml. of acetone. To this material were 3-methyl-5-pyrazolone showed no water-bleeding whatsoever, whereas h sodium salt f the f acid f f added 74.2 ml. of 0.5 N sulfunc acid and 10.4 grams of the same dye showed considerable water-bleeding. N,N- dibenzyl N,N,N"- trimethyl diethylenetriaminc.

Example 2 grams of the free acid form of the metal'dye lake The acetone solution was evaporated to dryness on the x2? gg g ggg 1E gisfgg' gg gfgigg steam bath, and the product dried in an air oven, ground methy1di6thy1enetriamine and tested as in Example 1. The same results were ob- The material was warmed on the steam bath until the tained.

Example 5.

CH: 1 Hz a H 100 mg. of the-free acid form of the chrome complex of the dye: 5-nitro-2-aminophenol 3-methyl-5-pyrazolone and 70 mg. 50% excess over theory) of N,N"-dibenzyl- N,N',N-trimethyl-di-(1,2-propylene)-triamine were added to cc, of methanol and the material incorporated into the nitrocellulose lacquer exactly as in the application of the dye in Example 1. The same results were obtained as in the previous examples.

Lacquers other than those mentioned may be used with the dyes in question, i. e., lacquers containing cellulose esters, such as cellulose formate, cellulose propionate, cellulose butyrate, cellulose-acetate-propionate, celluloseacetate-butyrate, or cellulose ethers, such as cellulose methyl ether, cellulose ethyl ether, cellulose benzyl ether and the like, including the usual vinyl resin lacquers.

l-CHPCHFIFH wherein Ar is a' phenyl radical, R is a lower aliphatic radical, R is a lower alkylene radical, Me represents a trivalent metal ion selected from the group consisting of chromium and cobalt, Y represents a radical selected from the class consisting of hydrogen, lower alkyl, cyano and nitro radicals, and Z and Z represent residues of coupling components of which the formulae are Z -OH and Z OH, said residues being free of carboxylic and sulfonic groups and selected from the class consisting of phenols-and naphthols containing a phenolic OH group in ortho position to the azo bridge after coupling and prior to the formation of the metal-dye complex, and enolizable keto compounds containing an enolic -OH group attached to the carbon atom in ortho position to the carbon atom bearing the azo group after coupling and prior to the formation of the metal-dye complex.

2. A metallized monoazo dyestuif characterized by the following formula:

CHs

3. A metallized monoazo dyestufi characterized by the following formula:

4. A metallized monoazo dyestufl characterized by the following formula:

5. A metallized monoazo dyestufi characterized by the 6. A metallized monoazo dyestufi characterized by the following formula:

References Cited in the file of this patent UNITED STATES PATENTS 1,800,300 Kranzlein Apr. 14, 1931 2,038,298 Kiernan Apr. 21, 1936 2,215,105 Krzikalla Sept. 17, 1940 2,539,212 Strobel Jan. 23, 1951 2,555,603 Ogilvie June 5, 1951 2,565,898 Widmer et al Aug. 28, 1951 2,619,502 Williams Nov. 25, 1952 2,628,960 Freyermuth Feb. 17, 1953 

1. METALLIZED MONOAZO DYESTUFFS SELECTED FROM THE CLASS CONSISTING OF THOSE HAVING THE FOLLOWING FORMULAE: 